Anthracene coloring-matters and process of making them.



"UNITED STATES, reruns: curios.

MAX HENRY ISLER, 0F MANNHEIM, AND PAUL NAVVIASKY, OF LUDWIGSHAFEN-ON- THE-RHINE, GERMANY, ASSIGNORS T0 BADISGHE ANILIN & SODA FABRIK, OF LUDWIGSHAFEN-ON THE-RHINE, GERMANY, A CORPORATION.

- ANTHRACENE GOLORING-MATTERS AND PROCESS OF MAKING THEM.

No Drawing.

tion.

'We have found that by treating orthohalogen-benzoyl-Q-amino-anthraquinone, or derivatives thereof, with a body having an alkaline reaction, such for instance as sodium carbonate, sodium bicarbonate, potassium carbonate, and the like, they can obtain new condensation products Which will dye extremely fast shades on cotton' and wool from a .hydrosulfite vat. The aforesaid treatment is preferably carried out in the presence of an indifferent solvent, such as nitrobenzene or naphthalene, and it is also advantageous to have a catalytic agent, such as copper, copper oxid, or copper chlorid, present during the reaction.

The ortho halogen -benzoyl 2 amino anthraqulnone compounds wh ch are used, as

aforesaid, for the production of the coloring mattersv can be obtained, for instance, by boiling a 2-amino-anthraquinone body with an ortho-halogen-benzoyl-halogenid, or a derivative .thereof, in the presence of nitro benzene.

Under the term a Q-amino-anthraquinone body, We include 2-arnino-anthraquinone itself and also such compounds as 2,0- diamino-anthraquinone, 2.7-diamino-anthraquinone, 2-amino-G-chlor-anthraquinone, 2- amino-6-hydroxy-anthraquinone, and a1nino-7-hydroxy-anthraquinone. Under the term derivative of ortho-halogenbenzoylhalogenid we include such compounds for instance as nitro-, halogenand methoxyderivatives.

Dur new coloring matters are characterized by containing nitrogen and being diflicultly soluble in the ordinary solvents, but they are soluble in concentrated sulfuric acid yielding from blue to green solutions,

which lose their blue to green color on the addition of strong nitric acid, and from the l Specification of Letters Patent.

Patented Mar. as, 1913'.

Application filed July 1, 1.91 1. Serial No. 636,491.

hydrosulfite vat the new coloring matters invention can be carried into practical effect, but our invention is not confined to these examples. The parts are by Weight.

Example 1: Boil. together ten parts of ortho chlor-benzoyl-Q-amino-antliraquinone (obtainable by boiling 2-amino-anthraquinone with ortho-chlor-benzoyl-chlorid in the presence of nitrobenzene), twenty-five parts of nitrobenzene, or of naphthalene, one-fifth of a part of cuprous chlorid, and three parts of calcined sodium carbonate, until a test portion shows that the formation of coloring matter is complete. Filter the reaction mass at a temperature of from eighty to ninety degrees centigra'de and Wash the coloring matter with alcohol and then with dilute hydrochloric acid. The coloring matter thus obtained yields a greenish blue solution in sulfuric acid and, on the addition of Water to this solution the coloring matter can be obtained in the orm of a red paste which is insoluble in Water and dilute caustic soda solution and alcohol. This paste can be used directly for dyeing and, from a hydrosulfite vat, yields, on cotton, reddish orange shades of great fastness. It is not necessary to isolate the chlorbenzoyl-amino-anthraquinone, as the formation of coloring matter can be carried out, if desired, in the nitrohenzene solution in which the intermediate product has been produced. In a similar manner, other halogen-benzoyl-amino-anthraquinones can be employed in the manufacture of coloring matters according to this invention. l lxamplefl: Boil together, for a few hours in a reflux apparatus, twenty-five arts of 'nitrobenzcnc, one-fifth of a part 0 copper It is soluble in concentrated sulfuric acid,

' the color of'the solution being a pure blue,

. orange color.

in boiling nitrobenzene. The coloring mat- 1 is produced.

which on warming turns violet-blue. The addition of nitric acid to the sulfuric, ac d solution imparts a yellowish tinge to the solution. In a similar manner, the corresponding coloring matter can be obtained from QJ-diamino-anthraquinone.. Example 3-: Boil together ten parts of the benzoyl compound obtainable by boiling 2- a-mino'G-chlor-anthraquinone -with orthochlor-benzoyl-chlorid in nitrobenzene solution, one-fifth of a part of copper oxid, three parts of calcined sodium. carbonate, and twenty-five parts of nitrobenzene until the quantity of coloring matter 'present no longer increases. Then isolate the product as described in the foregoing Example 1. 1t yields a blue-green solution in concentrated sulfuric acid, which "on warming turns pure blue. The addition of nitric acid rendersthe solution colorless or yellow. From a hydrosulfite vat it dyes cotton orange color.

Example 4-: Convert ten parts of the benzoyl compound obtainable by boiling 2- amino-6-hydroxy-anthraquinone with orthochlor-benzoyl-chlorid in nitrobenzene solution, into coloring matter in the manner described in either of the foregoing examples. The product yields a blue solution in concentrated sulfuric acid and -dyes cotton It is very dilficultly soluble ter obtainable in a similar manner from 2- amino 7 hydroxy anthraquinone yields shades of a somewhat blue'r tinge.

Example 5: Boil together, for onehour in a reflux apparatus, ten parts of the reaction product of 2amino-anthraquinone on 2,4- dichlor-benzoyl-chlorid (obtainable, for in-- stance, from ZA-dichlor-benzoic acid. and

thionyl chlorid), one-fifth of a part of copper oxid, four parts of potassium carbonate and thirty-five parts of nitrobenzene, and then work up the result in the manner described in the foregoing Example 1.- The product is a yellowish red powder which yields a greenish-blue solution in concentrated sulfuric acid. It is diificultly soluble in the ordinary organicsolvents, and is insoluble in Water. '[t dyes cotton and wool, from the hydrosul ii ism, red-orange shades. If in this example, 2.5-d1chlor-benzoyl chlorid be employee. a similar coloring matter Example G- J'Ieat together, for one hour,

' V in a reflux air satus, in an oil-bath at two hundred and fifteen degrees centigrade, ten parts of the .prglnct'of the reaction of 2- 'chlor--metlioxy 5-brom-benzoyl chlorid on 2-amin o-anthraquinone in the presence of nitrobenzcne, one-fifth of a part of copper oxid, four parts of potassium carbonate, and thirty-five parts of nitrobenzene, and work up the product as-described in the foregoing Example 1. It consists of a crystalline pow der which yields a green-blue solution in concentrated sulfuric acid and dyes cotton and wool, from the vat, red-orange shades. The 2-chlor-4-methoxy -5-brom-benzoyl chlorid, employed according to this example, can

be obtained by brominating .Z-acetaminoi methoxy toluol, oxidizing with permanganate, splitting off the acetyl group and replacing the free amino group by chlorin, and then treating the 2-chlor-4m1ethoxy-5- brom-benzoic acid with thionyl chlorid.

Example 7: Heat together, forone hour, in a reflux apparatus in an oil-bath at two hundred and fifteen dc rees centigrade. ten parts of the product 0 tainable by boiling 2 chlor 5 nitro benzoyl chlorid with 2- amino-anthraquinone in nitrobenz'ene, onefifth of a part of copper powder, three parts of potassium'carbonate and thirty-five parts of nitrobenzene, and then isolate the coloring matter as described in the foregoing Exters of the anthraquinone series by treating.

ortho-chlor-benzoyl 2-amino-anthraquinone with sodium carbonate in the presence of-nitrobenze'ne and cuprous chlorid.

, 3. As new articles of manufacture the coloring matters of the anthracene series which can be obtained by treatin an ortho-halogen benzoyl 2 amino ant raquinone body with a body having an alkaline reaction, in

the presence of a catalytic agent, which new coloring matters contain nitrogen and are difi'icultly soluble inthe ordinary solvents but are soluble in concentrated sulfuric acid yielding from blue to green solutions, which lose their blue to green color, on the addition of strong nitric acid, and which new coloring matters dye cotton, from the hydrosulfite vat, from orange to redorange shades of excellent fastness.

4. As a new article of manufacture the coloring matter of the anthracene series which can be obtained by'treating orthochlor-benzoyl-2-amino anthraquinone with sodium carbonate in the presenceof nitrobenzene and cuprous chlorid,which coloring matter contains nitrogen and is difiicultly soluble 111 the ordinary solvents,butis soluble in concentrated sulfuric acid yielding a.

i In testimony whereof we have hereunto set our hands in the presence of two sub scribing WitHQSSGS 1 MAX HENRY ISL'ER.

1 PAUL NAWIASKYM V '1 G. EHIILIARD'L, J. AL-nc. LLOYD. 

